Blue dyeing azodyestuffs



Patented Feb. 25, 1936 UNITED STATES PATENT OFFICE BLUE DYEIN G AZODYESTUFFS Grald Bonhote, Basel, and Carl Apotheker, Rieh en, near Basel, Switzerland, assignors to Society of Chemical Industry in Basic, Basel,

Switzerland No Drawing. Application March 13, 1935, Serial No. 10,960. In Switzerland April 14, 1934 6 Claims. (01. 260-) in which R represents an aromatic nucleus of the benzene series and both X's are ethoxy.

This invention relates to an improvement in or a modification of that described in the aforesaid application. By this invention new blue dyestuffs are obtained which have the same valuable properties as are possessed by the dyestuffs produced by the process of the aforesaid application and are made by coupling the diazo-compound of the foregoing general formula with an arylide of 2,3- hydroxynaphthoic acid of the general formula in which the positions 2, 4 and 6 of the arylide radical are occupied by hydrogen atoms, and in which further at least one of the positions 3 or 5 is substituted by a substituent which does not provoke solubility of the arylide in water. Such radicals, in contradistinction to radicals such as SOsI-I, COOH, OH, SOzH, and the like, are radicals such as halogen, alkyl or alkoxy. Such arylides are, for example, the meta-toluidide, the meta-chloranilide, the meta-nitranilide, the meta-bromanilide, the meta-iodoanilide of the 2,3-hydroxynaphthoic acid. Products falling also under the above definition are the arylides from 2,3-hydroxynaphthoic acid and 1-amino-3,5-dichlorobenzene.

The new dyestufis correspond to the general formula 5 CzHaO- ll N 2 3 l5 0-: 1 4 u I@ o n in which R. represents a nucleus of the benzene series, and in which the positions 2, 4 and 6 of the 20 arylide radical are substituted by hydrogen atoms and at least one of the positions 3 or 5 is substituted by another substituent. The new dyestuffs are dark, violet to blue powders insoluble in water but dissolving in sulfuric acid to blue solutions, 25 and in pyridine to violet solutions, and dyeing the fiber fast blue tints. It is remarkable here that the nature of the substituents in 3- or 5-position of the arylide nucleus has no essential effect on the shades and properties of the dyestuif. The 30 position of the substituent, however, is of considerable importance.

Particularly valuable dyeings are obtained when cotton, wool or silk is grounded, by known methods, with one of the aforesaid arylides and then 35 the latter is coupled with one of the aforesaid diazo-compounds.

The following examples illustrate the invention, the parts being by weight:- 40

, Example 1 Cotton yarn is impregnated with a solution containing per litre 5.5 grams of 2,3-hydroxynaphthoic acid 3'-methylanilide, 10 cc. of caustic 45 soda solution of 34 B., 10 cc. of Turkey red oil; the yarn is thoroughly wrung out and developed in a diazo solution containing 2 grams per litre of 4-phenoxy-acetylamino 2,5 diethoxy-l-aminobenzene. There is produced a pure blue tint 50 of very good properties of" fastness.

V The new dyestuff has the following constitution A blue tint of very good fastness to light. is

also obtained when the 3-chlora.nilide hydroxynaphthoic acid is used.

" Example 2;.

Cotton yarn is grounded with an alkaline solution containing per litre 7 grams of 2;3-hydroxy- 'Iiaphthoic acid 3-methylanilide and well wrung out; it is then developed in. a solution containing per litre 2 grams of diaz'oti'zed 4(2'-methyl) I phenoxy-acetylamino-Z,5-diethoxy-1- aminobenzene. A pure blue of very good fastness to light is produced. 7 g

Like'blue tints are obtained when 2,3-hydroxynaphthoic acid 3'-chlora nilide is used.

the formula; 1

The dyestufis ofthis example correspond to in which. :1: stands for CH3 or C1. The propersimilar.

. Example 3 ties of 'fastness or the. two dyestufisfare very The procedure is similar with the arylides of the 2,3-hydroxynaphthoic acid cited in the preamble. Valuable dyestufis are also obtained when using diazotizing components suchas, for example; 4'-(2 4 methyl) phenoxyacetylamino- 2,5 diethoxy 1 aminobenzene, 4-(4-methy1)- phenoxyacetylamino-2,5 tliethoxy-l-aminoben zene, 4-(2'-chloro) -phenoXyacetylamino-2,5 diethoxy- 1 -aminobenzene, 4-(2- methoxy) phenoxyacetylamino-2,5 diethoxyl-aminobenzene, 4- (3 '-bromo) -phenoxyacetylamino-2,5-diethoxy- 1 aminobenzene, 4 -(4" -ethoXy) -phenoxyacetylamino 2,5 diethdxy l ariiinoben'zene, 4 -(4- in chloro) -phenoxyacetylamino-2,5-diethoxy-l-aminobenzene, 4-(4' methylsulfone) phenoxyacetylamino-2",5-diethoxy-l aminobenzene and the like. 7 r

What we claim is: V I. The dyestufisof the general formula in which R1 represents an aromatic nucleus of the benzene jseri'e's and x standsffon halogen, alkyl or 'al'koxy, which products are 'dark blue powdersinsoluble in waterbut dissolving. in pyridine to iolet solutions, and. in sulfuric acid toblue-solutions; and dye the cotton fib'er fast blue tints"; r

2. The dyestufis of 'theigeneraliformulw halogen l'.

in which R1 represents an aromatic nucleus of the benzene: "series,v which products are dark'. blue powders insoluble in water, but dissolving in pyridine to violet solutions, and in suifuriciacid to blue solutions, and dye cotton fiber fast blue tints.

3. The dyestuirs of the general formula Rx-O-CHz-(fi-NH CgHsO N H N 0H III ()1 CN H 11 l O H in which R1 represents an aromatic nucleus of the benzene series, which products are dark blue powders insoluble in water, but dissolving in pyridine to violet solutions, and in sulfuric acid to blue solutions, and dye cotton fiber fast blue tints.

4. The dyestuffs of the general formula OH HI (EH! e O H I in which R1 represents an aromatic nucleus of the benzene series, which products are dark blue powders insoluble in water, but dissolving in pyridine to violet solutions, and in sulfuric acid to blue solutions, and dye the cotton fiber fast blue tints.

5. The dyestuff of the formula.

which product is a. dark blue powder insoluble in water, but dissolving in pyridine to a violet solution and in sulfuric acid to a blue solution, 0

and dyes the cotton fiber fast blue tints.

6. The dyestufi of the formula which product is a dark blue powder insoluble in water, but dissolving in pyridine to a violet solution and in sulfuric acid to a blue solution, and dyes the cotton fiber fast blue tints.

GERALD BONHOTE. CARL APOTHEKER. 

